U.S. patent application number 10/745785 was filed with the patent office on 2004-07-15 for catalyst composition and methods for its preparation and use in a polymerization process.
Invention is credited to Wenzel, Timothy T..
Application Number | 20040138057 10/745785 |
Document ID | / |
Family ID | 32716627 |
Filed Date | 2004-07-15 |
United States Patent
Application |
20040138057 |
Kind Code |
A1 |
Wenzel, Timothy T. |
July 15, 2004 |
Catalyst composition and methods for its preparation and use in a
polymerization process
Abstract
The present invention relates to a catalyst composition and a
method for making the catalyst composition of a polymerization
catalyst and an organic polyhydroxyl compound. The invention is
also directed to the use of the catalyst composition in the
polymerization of olefin(s). In particular, the polymerization
catalyst system is supported on a carrier. More particularly, the
polymerization catalyst comprises a bulky ligand metallocene-type
catalyst system.
Inventors: |
Wenzel, Timothy T.;
(Charleston, WV) |
Correspondence
Address: |
Univation Technologies, LLC
Suite 1950
5555 San Felipe
Houston
TX
77056
US
|
Family ID: |
32716627 |
Appl. No.: |
10/745785 |
Filed: |
December 23, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10745785 |
Dec 23, 2003 |
|
|
|
09434725 |
Nov 5, 1999 |
|
|
|
60113034 |
Dec 21, 1998 |
|
|
|
Current U.S.
Class: |
502/150 ;
502/103; 502/117; 502/152; 502/172 |
Current CPC
Class: |
C08F 4/65916 20130101;
C08F 10/00 20130101; C08F 10/00 20130101; C08F 4/65927 20130101;
C08F 4/6494 20130101; C08F 10/00 20130101; C08F 4/65912
20130101 |
Class at
Publication: |
502/150 ;
502/117; 502/103; 502/152; 502/172 |
International
Class: |
B01J 031/00 |
Claims
We claim:
1. A catalyst composition comprising, in combination, a
polymerization catalyst and an organic polyhydroxyl compound.
2. The catalyst composition of claim 1 wherein the polymerization
catalyst comprises a conventional-type transition metal catalyst
compound.
3. The catalyst composition of claim 1 wherein the polymerization
catalyst comprises a bulky ligand metallocene-type catalyst
compound.
4. The catalyst composition of a claim 1 wherein the organic
polyhydroxyl compound is represented by the general formula:
R(R'R"C--OH).sub.3+x where x is greater than 0, R has from 1 to
1000 non-hydrogen atoms, and R' and R", independently, can be
hydrogen or from 0 to 1000 non-hydrogen atoms.
5. The catalyst composition of claim 1 wherein the organic
polyhydroxyl compound has three or more adjacent hydroxyl
groups.
6. The catalyst composition of claim 1 wherein the organic
polyhydroxyl compound is a sugar derived complex.
7. The catalyst composition of claim 4 wherein x is 2 or
greater.
8. The catalyst composition of claim 1 wherein the polymerization
catalyst is supported.
9. The catalyst composition of claim 1 wherein the weight percent
of the organic polyhydroxyl compound based on the total weight of
the polymerization catalyst is in the range of from 0.1 weight
percent to about 100 weight percent.
10. A method of making a catalyst composition, the method
comprising the steps of combining: (a) a polymerization catalyst;
and (b) an organic polyhydroxyl compound.
11. The method of claim 10 wherein the polymerization catalyst
comprises a conventional-type transition metal catalyst
compound.
12. The method of claim 10 wherein the polymerization catalyst
comprises a bulky ligand metallocene-type catalyst compound.
13. The method of a claim 10 wherein the polymerization catalyst
comprises a carrier.
14. The method of a claim 10 wherein the organic polyhydroxyl
compound is represented by the formula: R(R'R"C--OH).sub.3+x where
x is greater than 0, R has from 1 to 1000 non-hydrogen atoms, and
R' and R", independently, can be hydrogen or from 0 to 1000
non-hydrogen atoms.
15. The method of claim 10 wherein the weight percent of the
organic polyhydroxyl compound based on the total weight of the
polymerization catalyst is in the range of from 0.1 weight percent
to about 100 weight percent.
16. The method of claim 14 wherein x is 2 or greater.
17. The method of claim 10 wherein the organic polyhydroxyl
compound has a melting point is greater than 50.degree. C.
18. The method of claim 10 wherein the mixing period of time is
from 10 minutes to about 48 hours.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a divisional of U.S. patent
application Ser. No. 09/434,725, filed Nov. 5, 1999, now issued as
U.S. Pat. No. ______, which claims priority from Provisional U.S.
Application Serial No. 60/113,034 filed Dec. 21, 1998, and is
herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a catalyst composition and
methods for preparing the catalyst composition and for its use in a
process for polymerizing olefins. In particular, the invention is
directed to a method for preparing a catalyst composition of a
bulky ligand metallocene-type catalyst system and/or a
conventional-type transition metal catalyst system and an organic
polyhydroxyl compound.
BACKGROUND OF THE INVENTION
[0003] Advances in polymerization and catalysis have resulted in
the capability to produce many new polymers having improved
physical and chemical properties useful in a wide variety of
superior products and applications. With the development of new
catalysts the choice of polymerization-type (solution, slurry, high
pressure or gas phase) for producing a particular polymer has been
greatly expanded. Also, advances in polymerization technology have
provided more efficient, highly productive and economically
enhanced processes. Especially illustrative of these advances is
the development of technology utilizing bulky ligand
metallocene-type catalyst systems. Regardless of these
technological advances in the polyolefin industry, common problems,
as well as new challenges associated with process operability still
exist. For example, the tendency for a gas phase or slurry phase
process to foul and/or sheet remains a challenge.
[0004] For example, in a continuous slurry process fouling on the
walls of the reactor, which act as a heat transfer surface, can
result in many operability problems. Poor heat transfer during
polymerization can result in polymer particles adhering to the
walls of the reactor. These polymer particles can continue to
polymerize on the walls and can result in a premature reactor
shutdown. Also, depending on the reactor conditions, some of the
polymer may dissolve in the reactor diluent and redeposit on for
example the metal heat exchanger surfaces.
[0005] In a typical continuous gas phase process, a recycle system
is employed for many reasons including the removal of heat
generated in the process by the polymerization. Fouling, sheeting
and/or static generation in a continuous gas phase process can lead
to the ineffective operation of various reactor systems. For
example, the cooling mechanism of the recycle system, the
temperature probes utilized for process control and the distributor
plate, if affected, can lead to an early reactor shutdown.
[0006] Evidence of, and solutions to, various process operability
problems have been addressed by many in the art. For example, U.S.
Pat. Nos. 4,792,592, 4,803,251, 4,855,370 and 5,391,657 all discuss
techniques for reducing static generation in a polymerization
process by introducing to the process for example, water, alcohols,
ketones, and/or inorganic chemical additives; European Patent EP 0
634 421 B1 discusses introducing directly into the polymerization
process water, alcohol and ketones to reduce fouling. A PCT
publication WO 97/14721 published Apr. 24, 1997 discusses the
suppression of fines that can cause sheeting by adding an inert
hydrocarbon to the reactor; U.S. Pat. No. 5,627,243 discusses a new
type of distributor plate for use in fluidized bed gas phase
reactors; PCT publication WO 96/08520 discusses avoiding the
introduction of a scavenger into the reactor; U.S. Pat. No.
5,461,123 discusses using sound waves to reduce sheeting; U.S. Pat.
No. 5,066,736 and EP-A1 0 549 252 discuss the introduction of an
activity retarder to the reactor to reduce agglomerates; U.S. Pat.
No. 5,610,244 relates to feeding make-up monomer directly into the
reactor above the bed to avoid fouling and improve polymer quality;
U.S. Pat. No. 5,126,414 discusses including an oligomer removal
system for reducing distributor plate fouling and providing for
polymers free of gels; EP-A1 0 453 116 published Oct. 23, 1991
discusses the introduction of antistatic agents to the reactor for
reducing the amount of sheets and agglomerates; U.S. Pat. No.
4,012,574 discusses adding a surface-active compound, a
perfluorocarbon group, to the reactor to reduce fouling; U.S. Pat.
No. 5,026,795 discusses the addition of an antistatic agent with a
liquid carrier to the polymerization zone in the reactor; U.S. Pat.
No. 5,410,002 discusses using a conventional Ziegler-Natta
titanium/magnesium supported catalyst system where a selection of
antistatic agents are added directly to the reactor to reduce
fouling; U.S. Pat. Nos. 5,034,480 and 5,034,481 discuss a reaction
product of a conventional Ziegler-Natta titanium catalyst with an
antistat to produce ultrahigh molecular weight ethylene polymers;
U.S. Pat. No. 3,082,198 discusses introducing an amount of a
carboxylic acid dependent on the quantity of water in a process for
polymerizing ethylene using a titanium/aluminum organometallic
catalysts in a hydrocarbon liquid medium; and U.S. Pat. No.
3,919,185 describes a slurry process using a nonpolar hydrocarbon
diluent using a conventional Ziegler-Natta-type or Phillips-type
catalyst and a polyvalent metal salt of an organic acid having a
molecular weight of at least 300.
[0007] There are various other known methods for improving
operability including coating the polymerization equipment, for
example, treating the walls of a reactor using chromium compounds
as described in U.S. Pat. Nos. 4,532,311 and 4,876,320; injecting
various agents into the process, for example PCT Publication WO
97/46599 published Dec. 11, 1997 discusses feeding into a lean zone
in a polymerization reactor an unsupported, soluble
metallocene-type catalyst system and injecting antifoulants or
antistatic agents into the reactor; controlling the polymerization
rate, particularly on start-up; and reconfiguring the reactor
design.
[0008] Others in the art to improve process operability have
discussed modifying the catalyst system by preparing the catalyst
system in different ways. For example, methods in the art include
combining the catalyst system components in a particular order;
manipulating the ratio of the various catalyst system components;
varying the contact time and/or temperature when combining the
components of a catalyst system; or simply adding various compounds
to the catalyst system. These techniques or combinations thereof
are discussed in the literature. Especially illustrative in the art
is the preparation procedures and methods for producing bulky
ligand metallocene-type catalyst systems, more particularly
supported bulky ligand metallocene-type catalyst systems with
reduced tendencies for fouling and better operability. Examples of
these include: WO 96/11961 published Apr. 26, 1996 discusses as a
component of a supported catalyst system an antistatic agent for
reducing fouling and sheeting in a gas, slurry or liquid pool
polymerization process; U.S. Pat. No. 5,283,218 is directed towards
the prepolymerization of a metallocene catalyst; U.S. Pat. Nos.
5,332,706 and 5,473,028 have resorted to a particular technique for
forming a catalyst by incipient impregnation; U.S. Pat. Nos.
5,427,991 and 5,643,847 describe the chemical bonding of
non-coordinating anionic activators to supports; U.S. Pat. No.
5,492,975 discusses polymer bound metallocene-type catalyst
systems; U.S. Pat. No. 5,661,095 discusses supporting a
metallocene-type catalyst on a copolymer of an olefin and an
unsaturated silane; PCT publication WO 97/06186 published Feb. 20,
1997 teaches removing inorganic and organic impurities after
formation of the metallocene-type catalyst itself; PCT publication
WO 97/15602 published May 1, 1997 discusses readily supportable
metal complexes; PCT publication WO 97/27224 published Jul. 31,
1997 relates to forming a supported transition metal compound in
the presence of an unsaturated organic compound having at least one
terminal double bond; and EP-A2-811 638 discusses using a
metallocene catalyst and an activating cocatalyst in a
polymerization process in the presence of a nitrogen containing
antistatic agent.
[0009] While all these possible solutions might reduce the level of
fouling or sheeting somewhat, some are expensive to employ and/or
may not reduce fouling and sheeting to a level sufficient to
successfully operate a continuous process, particularly a
commercial or large-scale process.
[0010] Thus, it would be advantageous to have a polymerization
process capable of operating continuously with enhanced reactor
operability and at the same time produce new and improved polymers.
It would also be highly beneficial to have a continuously operating
polymerization process having more stable catalyst productivities,
reduced fouling/sheeting tendencies and increased duration of
operation.
SUMMARY OF THE INVENTION
[0011] This invention provides a method of making a new and
improved catalyst composition and for its use in a polymerizing
process. The method comprises the step of combining, contacting,
blending and/or mixing a catalyst system, preferably a supported
catalyst system, with an organic polyhydroxyl compound. In one
embodiment the catalyst system comprises a conventional-type
transition metal catalyst compound. In the most preferred
embodiment the catalyst system comprises a bulky ligand
metallocene-type catalyst compound. The combination of the catalyst
system and the organic polyhydroxyl compound is useful in any
olefin polymerization process. The preferred polymerization
processes are a gas phase or a slurry phase process, most
preferably a gas phase process.
[0012] In an embodiment, the invention provides for a method of
making a catalyst composition useful for the polymerization of
olefin(s), the method including combining, contacting, blending
and/or mixing a polymerization catalyst with at least one organic
polyhydroxyl compound. In an embodiment, the polymerization
catalyst is a conventional-type transition metal polymerization
catalyst, more preferably a supported conventional-type transition
metal polymerization catalyst. In the most preferred embodiment,
the polymerization catalyst is a bulky ligand metallocene-type
catalyst, most preferably a supported bulky ligand metallocene-type
polymerization catalyst.
[0013] In one preferred embodiment, the invention is directed to a
catalyst composition comprising a catalyst compound, preferably a
conventional-type transition metal catalyst compound, more
preferably a bulky ligand metallocene-type catalyst compound, an
activator and/or cocatalyst, a carrier, and a organic polyhydroxyl
compound.
[0014] In the most preferred method of the invention, the organic
polyhydroxyl compound is blended, preferably dry blended, and most
preferably tumble dry blended or fluidized, with a supported
catalyst system or polymerization catalyst comprising a carrier. In
this most preferred embodiment, the polymerization catalyst
includes at least one bulky ligand metallocene-type catalyst
compound, an activator and a carrier.
[0015] In yet another embodiment, the invention relates to a
process for polymerizing olefin(s) in the presence of a catalyst
composition comprising a polymerization catalyst and a organic
polyhydroxyl compound, preferably the polymerization catalyst
comprises a carrier, more preferably the polymerization catalyst
comprises one or more of combination of a conventional-type
catalyst compound and/or a bulky ligand metallocene-type catalyst
compound.
[0016] In a preferred method for making the catalyst composition of
the invention, the method comprises the steps of combining a bulky
ligand metallocene-type catalyst compound, an activator and a
carrier to form a supported bulky ligand metallocene-type catalyst
system, and contacting the supported bulky ligand metallocene-type
catalyst compound with a organic polyhydroxyl compound. In the most
preferred embodiment, the supported bulky ligand metallocene-type
catalyst system and the organic polyhydroxyl compound are in a
substantially dry state or dried state.
[0017] In an embodiment, the invention provides for a process for
polymerizing olefin(s) in the presence of a polymerization catalyst
having been combined, contacted, blended, or mixed with at least
one organic polyhydroxyl compound.
[0018] In another preferred embodiment, the invention provides for
a process for polymerizing olefin(s) in a reactor in which a
organic polyhydroxyl compound has been introduced prior to the
introduction of the polymerization catalyst and/or the organic
polyhydroxyl compound is simultaneously introduced into the reactor
with the polymerization catalyst.
DETAILED DESCRIPTION OF THE INVENTION
[0019] Introduction
[0020] The invention is directed toward a method for making a
catalyst composition and to the catalyst composition itself. The
invention also relates to a polymerization process having improved
operability and product capabilities using the catalyst
composition. It has been suprisingly discovered that using a
organic polyhydroxyl compound in combination with a catalyst system
results in a substantially improved polymerization process.
Particularly surprising is where the catalyst system is supported
on carrier, more so where the catalyst system includes a bulky
ligand metallocene-type catalyst system, and even more so where the
bulky ligand metallocene-type catalysts are very active and/or are
highly incorporating of comonomer.
[0021] Utilizing the polymerization catalysts described below in
combination with a organic polyhydroxyl compound results in a
substantial improvement in process operability, a significant
reduction in sheeting and fouling, improved catalyst performance,
better polymer particle, and the capability to produce a broader
range of polymers.
[0022] Catalyst Components and Catalyst Systems
[0023] All polymerization catalysts including conventional-type
transition metal catalysts are suitable for use in the polymerizing
process of the invention. However, processes using bulky ligand
and/or bridged bulky ligand, metallocene-type catalysts are
particularly preferred. The following is a non-limiting discussion
of the various polymerization catalysts useful in the
invention.
[0024] Conventional-Type Transition Metal Catalysts
[0025] Conventional-type transition metal catalysts are those
traditional Ziegler-Natta catalysts and Phillips-type chromium
catalyst well known in the art. Examples of conventional-type
transition metal catalysts are discussed in U.S. Pat. Nos.
4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359
and 4,960,741 all of which are herein fully incorporated by
reference. The conventional-type transition metal catalyst
compounds that may be used in the present invention include
transition metal compounds from Groups III to VIII, preferably IVB
to VIB of the Periodic Table of Elements.
[0026] These conventional-type transition metal catalysts may be
represented by the formula: MR.sub.x, where M is a metal from
Groups IIIB to VIII, preferably Group IVB, more preferably
titanium; R is a halogen or a hydrocarbyloxy group; and x is the
valence of the metal M. Non-limiting examples of R include alkoxy,
phenoxy, bromide, chloride and fluoride. Non-limiting examples of
conventional-type transition metal catalysts where M is titanium
include TiCl.sub.4, TiBr.sub.4, Ti(OC.sub.2H.sub.5).sub.3Cl,
Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OC.sub.4H.sub.9).sub.3Cl,
Ti(OC.sub.3H.sub.7).sub.2Cl.sub.2,
Ti(OC.sub.2H.sub.5).sub.2Br.sub.2, TiCl.sub.3.1/3A1Cl.sub.3 and
Ti(OC.sub.12H.sub.25)Cl.sub.3.
[0027] Conventional-type transition metal catalyst compounds based
on magnesium/titanium electron-donor complexes that are useful in
the invention are described in, for example, U.S. Pat. Nos.
4,302,565 and 4,302,566, which are herein fully incorporate by
reference. The MgTiCl.sub.6 (ethyl acetate).sub.4 derivative is
particularly preferred. British Patent Application 2,105,355 and
U.S. Pat. No. 5,317,036, herein incorporated by reference,
describes various conventional-type vanadium catalyst compounds.
Non-limiting examples of conventional-type vanadium catalyst
compounds include vanadyl trihalide, alkoxy halides and alkoxides
such as VOCl.sub.3, VOCl.sub.2(OBu) where Bu=butyl and
VO(OC.sub.2H.sub.5).sub.3; vanadium tetra-halide and vanadium
alkoxy halides such as VCl.sub.4 and VCl.sub.3(OBu); vanadium and
vanadyl acetyl acetonates and chloroacetyl acetonates such as
V(AcAc).sub.3 and VOCl.sub.2(AcAc) where (AcAc) is an acetyl
acetonate. The preferred conventional-type vanadium catalyst
compounds are VOCl.sub.3, VCl.sub.4 and VOCl.sub.2--OR where R is a
hydrocarbon radical, preferably a C.sub.1 to C.sub.10 aliphatic or
aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl,
butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl,
cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates.
[0028] Conventional-type chromium catalyst compounds, often
referred to as Phillips-type catalysts, suitable for use in the
present invention include CrO.sub.3, chromocene, silyl chromate,
chromyl chloride (CrO.sub.2Cl.sub.2), chromium-2-ethyl-hexanoate,
chromium acetylacetonate (Cr(AcAc).sub.3), and the like.
Non-limiting examples are disclosed in U.S. Pat. Nos. 3,709,853,
3,709,954, 3,231,550, 3,242,099 and 4,077,904, which are herein
fully incorporated by reference.
[0029] Still other conventional-type transition metal catalyst
compounds and catalyst systems suitable for use in the present
invention are disclosed in U.S. Pat. Nos. 4,124,532, 4,302,565,
4,302,566, 4,376,062, 4,379,758, 5,066,737 and 5,763,723 and
published EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all
herein incorporated by reference. The conventional-type transition
metal catalysts of the invention may also have the general formula
M'.sub.1M"X.sub.2tY.sub.uE, where M' is Mg, Mn and/or Ca; t is a
number from 0.5 to 2; M" is a transition metal Ti, V and/or Zr; X
is a halogen, preferably Cl, Br or I; Y may be the same or
different and is halogen, alone or in combination with oxygen,
--NR2, --OR, --SR, --COOR, or --OSOOR, where R is a hydrocarbyl
radical, in particular an alkyl, aryl, cycloalkyl or arylalkyl
radical, acetylacetonate anion in an amount that satisfies the
valence state of M'; u is a number from 0.5 to 20; E is an electron
donor compound selected from the following classes of compounds:
(a) esters of organic carboxylic acids; (b) alcohols; (c) ethers;
(d) amines; (e) esters of carbonic acid; (f) nitriles; (g)
phosphoramides, (h) esters of phosphoric and phosphorus acid, and
(j) phosphorus oxy-chloride. Non-limiting examples of complexes
satisfying the above formula include:
MgTiCl.sub.52CH.sub.3COOC.sub.2H.sub.5,
Mg.sub.3Ti.sub.2Cl.sub.12.7CH.sub- .3COOC.sub.2H.sub.5,
MgTiCl.sub.5.6C.sub.2H.sub.5OH, MgTiCl.sub.5 100CH.sub.3OH,
MgTiCl.sub.5 tetrahydrofuran, MgTi.sub.2
Cl.sub.12.7C.sub.6H.sub.5CN, Mg.sub.3Ti.sub.2Cl.sub.12
.6C.sub.6H.sub.5COOC.sub.2H.sub.5,
MgTiCl.sub.6.2CH.sub.3COOC.sub.2H.sub.- 5,
MgTiCl.sub.6.6C.sub.5H.sub.5N,
MgTiCl.sub.5(OCH.sub.3).sub.2CH.sub.3COO- C.sub.2H.sub.5,
MgTiCl.sub.5N(C.sub.6H.sub.5).sub.2.3CH.sub.3 COOC.sub.2H.sub.5,
MgTiBr.sub.2Cl.sub.4.2(C.sub.2H.sub.5).sub.2O,
MnTiCl.sub.5.4C.sub.2H.sub.5OH, Mg.sub.3V.sub.2Cl.sub.12.7CH.sub.3
COOC.sub.2H.sub.5, MgZrCl.sub.6.4 tetrahydrofuran. Other catalysts
may include cationic catalysts such as AlCl.sub.3, and other cobalt
and iron catalysts well known in the art. See for example U.S. Pat.
Nos. 4,472,559 and 4,182,814 incorporated herein by reference.
[0030] Typically, these conventional-type transition metal catalyst
compounds excluding some convention-type chromium catalyst
compounds are activated with one or more of the conventional-type
cocatalysts described below.
[0031] Conventional-Type Cocatalysts
[0032] Conventional-type cocatalyst compounds for the above
conventional-type transition metal catalyst compounds may be
represented by the formula
M.sup.3M.sup.4.sub.vX.sup.2.sub.cR.sup.3.sub.b-c, wherein M.sup.3
is a metal from Group Iowa, IIA, IIB and BL.sup.A of the Periodic
Table of Elements; M.sup.4 is a metal of Group IA of the Periodic
Table of Elements; v is a number from 0 to 1; each X.sup.2 is any
halogen; c is a number from 0 to 3; each R.sup.3 is a monovalent
hydrocarbon radical or hydrogen; b is a number from 1 to 4; and
wherein b minus c is at least 1. Other conventional-type
organometallic cocatalyst compounds for the above conventional-type
transition metal catalysts have the formula M.sup.3R.sup.3.sub.k,
where M.sup.3 is a Group IA, IIA, IIB or IIIA metal, such as
lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium,
and gallium; k equals 1, 2 or 3 depending upon the valency of
M.sup.3 which valency in turn normally depends upon the particular
Group to which M.sup.3 belongs; and each R.sup.3 may be any
monovalent hydrocarbon radical.
[0033] Non-limiting examples of conventional-type organometallic
cocatalyst compounds of Group IA, IIA and IIIA useful with the
conventional-type catalyst compounds described above include
methyllithium, butyllithium, dihexylmercury, butylmagnesium,
diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum,
diisobutyl ethylboron, diethylcadmium, di-n-butylzinc and
tri-n-amylboron, and, in particular, the aluminum alkyls, such as
tri-hexyl-aluminum, triethylaluminum, trimethylaluminum, and
tri-isobutylaluminum. Other conventional-type cocatalyst compounds
include mono-organohalides and hydrides of Group IIA metals, and
mono- or di-organohalides and hydrides of Group IIIA metals.
Non-limiting examples of such conventional-type cocatalyst
compounds include di-isobutylaluminum bromide, isobutylboron
dichloride, methyl magnesium chloride, ethylberyllium chloride,
ethylcalcium bromide, di-isobutylaluminum hydride, methylcadmium
hydride, diethylboron hydride, hexylberyllium hydride,
dipropylboron hydride, octylmagnesium hydride, butylzinc hydride,
dichloroboron hydride, di-bromo-aluminum hydride and bromocadmium
hydride. Conventional-type organometallic cocatalyst compounds are
known to those in the art and a more complete discussion of these
compounds may be found in U.S. Pat. Nos. 3,221,002 and 5,093,415,
which are herein fully incorporated by reference.
[0034] For purposes of this patent specification and appended
claims conventional-type transition metal catalyst compounds
exclude those bulky ligand metallocene-type catalyst compounds
discussed below. For purposes of this patent specification and the
appended claims the term "cocatalyst" refers to conventional-type
cocatalysts or conventional-type organometallic cocatalyst
compounds. Bulky ligand metallocene-type catalyst compounds and
catalyst systems for use in combination with a organic polyhydroxyl
compound of the invention are described below.
[0035] Bulky Ligand Metallocene-Type Catalyst Compounds
[0036] Generally, bulky ligand metallocene-type catalyst compounds
include half and full sandwich compounds having one or more bulky
ligands bonded to at least one metal atom. Typical bulky ligand
metallocene-type compounds are generally described as containing
one or more bulky ligand(s) and one or more leaving group(s) bonded
to at least one metal atom. For the purposes of this patent
specification and appended claims the term "leaving group" is any
ligand that can be abstracted from a bulky ligand metallocene-type
catalyst compound to form a bulky ligand metallocene-type catalyst
cation capable of polymerizing one or more olefins.
[0037] The bulky ligands are generally represented by one or more
open or fused ring(s) or ring systeM(s) or a combination thereof.
These ring(s) or ring systeM(s) are typically composed of atoms
selected from Groups 13 to 16 atoms, preferably the atoms are
selected from the group consisting of carbon, nitrogen, oxygen,
silicon, sulfur, phosphorous, boron and aluminum or a combination
thereof. Most preferably the ring(s) or ring systeM(s) are composed
of carbon atoms such as but not limited to those cyclopentadienyl
ligands or cyclopentadienyl-type ligand structures or other similar
functioning ligand structure such as a pentadiene, a
cyclooctatetraendiyl or an imide ligand. The metal atom is
preferably selected from Groups 3 through 16 and the lanthamide or
actinide series of the Periodic Table of Elements. Preferably the
metal is a transition metal from Groups 4 through 12, more
preferably 4, 5 and 6, and most preferably the metal is from Group
4.
[0038] In one embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention are represented by the
formula:
L.sup.AL.sup.BMQ.sub.n (1)
[0039] where M is a metal atom from the Periodic Table of the
Elements and may be a Group 3 to 12 metal or from the lanthamide or
actinide series of the Periodic Table of Elements, preferably M is
a Group 4, 5 or 6 transition metal, more preferably M is a Group 4
transition metal, even more preferably M is zirconium, hafnium or
titanium.
[0040] The bulky ligands, L.sup.A and L.sup.B, are open or fused
ring(s) or ring systeM(s) such as unsubstituted or substituted,
cyclopentadienyl ligands or cyclopentadienyl-type ligands,
heteroatom substituted and/or heteroatom containing
cyclopentadienyl-type ligands. Non-limiting examples of bulky
ligands include cyclopentadienyl ligands, indenyl ligands,
benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands,
cyclooctatetraendiyl ligands, azenyl ligands, azulene ligands,
pentalene ligands, phosphoyl ligands, pyrrolyl ligands, pyrozolyl
ligands, carbazolyl ligands, borabenzene ligands and the like,
including hydrogenated versions thereof, for example
tetrahydroindenyl ligands. In one embodiment, L.sup.A and L.sup.B
may be any other ligand structure capable of .eta.-5 bonding to M.
In another embodiment, L.sup.A and L.sup.B may comprise one or more
heteroatoms, for example, nitrogen, silicon, boron, germanium,
sulfur and phosphorous, in combination with carbon atoms to form an
open, or preferably a fused, ring or ring system, for example, a
hetero-cyclopentadienyl ancillary ligand. Other L.sup.A and L.sup.B
bulky ligands include but are not limited to bulky amides,
phosphides, alkoxides, aryloxides, imides, carbolides, borollides,
porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
Independently, each L.sup.A and L.sup.B may be the same or
different type of bulky ligand that is bonded to M. In one
embodiment in formula (I) only one of either L.sup.A or L.sup.B is
present.
[0041] Independently, each L.sup.A and L.sup.B may be unsubstituted
or substituted with a combination of substituent groups R.
Non-limiting examples of substituent groups R include one or more
from the group selected from hydrogen, or linear, branched, cyclic
alkyl radicals, or alkenyl, alkynl or aryl radicals, or combination
thereof. In a preferred embodiment, substituent groups R have up to
50 non-hydrogen atoms, preferably from 1 to 30 carbon atoms that
can also be substituted with halogens or heteroatoms or the like.
Non-limiting examples of alkyl substituents R include methyl,
ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl,
benzyl or phenyl groups and the like, including all their isomers,
for example tertiary butyl, isopropyl, and the like. Other
hydrocarbyl radicals include fluoromethyl, fluroethyl,
difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl
substituted organometalloid radicals including trimethylsilyl,
trimethylgermyl, methyldiethylsilyl and the like; and
halocarbyl-substituted organometalloid radicals including
tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,
bromomethyldimethylgermyl and the like; and disubstitiuted boron
radicals including dimethylboron for example; and disubstituted
pnictogen radicals including dimethylamine, dimethylphosphine,
diphenylamine, methylphenylphosphine, chalcogen radicals including
methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.
Non-hydrogen substituents R include the atoms carbon, silicon,
boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,
germanium and the like, including olefins such as but not limited
to olefinically unsaturated substituents including vinyl-terminated
ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the
like. Also, at least two R groups, preferably two adjacent R
groups, are joined to form a ring structure having from 3 to 30
atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon,
germanium, aluminum, boron or a combination thereof. Also, a
substituent group R group such as 1-butanyl may form a carbon sigma
bond to the metal M.
[0042] Other ligands may be bonded to the metal M, such as at least
one leaving group Q. In one embodiment, Q is a monoanionic labile
ligand having a sigma-bond to M. Depending on the oxidation state
of the metal, the value for n is 0, 1 or 2 such that formula (I)
above represents a neutral bulky ligand metallocene-type catalyst
compound.
[0043] Non-limiting examples of Q ligands include weak bases such
as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl
radicals having from 1 to 20 carbon atoms, hydrides or halogens and
the like or a combination thereof. In another embodiment, two or
more Q's form a part of a fused ring or ring system. Other examples
of Q ligands include those substituents for R as described above
and including cyclobutyl, cyclohexyl, heptyl, tolyl,
trifluromethyl, tetramethylene, pentamethylene, methylidene,
methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),
dimethylamide, dimethylphosphide radicals and the like.
[0044] In one embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention include those of formula I
where L.sup.A and L.sup.B are bridged to each other by a bridging
group, A. These bridged compounds are known as bridged, bulky
ligand metallocene-type catalyst compounds. Non-limiting examples
of bridging group A include bridging groups containing at least one
Group 13 to 16 atom, often referred to a divalent moiety such as
but not limited to at least one of a carbon, oxygen, nitrogen,
silicon, boron, germanium and tin atom or a combination thereof.
Preferably bridging group A contains a carbon, silicon or germanium
atom, most preferably A contains at least one silicon atom or at
least one carbon atom. The bridging group A may also contain
substituent groups R as defined above including halogens.
[0045] In another embodiment, the bulky ligand metallocene-type
catalyst compound of the invention is represented by the
formula:
(C.sub.5H.sub.4-dR.sub.d)A.sub.x(C.sub.5H.sub.4-dRd)MQg-.sub.2
(II)
[0046] where M is a Group 4, 5, 6 transition metal,
(C.sub.5H.sub.4-dR.sub.d) is an unsubstituted or substituted,
cyclopentadienyl ligand or cyclopentadienyl-type bulky ligand
bonded to M, each R, which can be the same or different, is
hydrogen or a substituent group containing up to 50 non-hydrogen
atoms or substituted or unsubstituted hydrocarbyl having from 1 to
30 carbon atoms or combinations thereof, or two or more carbon
atoms are joined together to form a part of a substituted or
unsubstituted ring or ring system having 4 to 30 carbon atoms, A is
one or more of, or a combination of, carbon, germanium, boron,
silicon, tin, phosphorous or nitrogen atom containing radical
bridging two (C.sub.5H.sub.4-dR.sub.d) rings; more particularly,
non-limiting examples of bridging group A may be represented by
R.sub.12C, R'.sub.1Si, R'.sub.2Si R'.sub.2Si, R'.sub.2Si R'.sub.2C,
R'.sub.2Ge, R'.sub.2Si R'.sub.2Ge, R'.sub.2GeR'.sub.2C, R'N, R'P,
R'.sub.2C R'N, R'.sub.2C R'P, R'.sub.2Si RN, R'.sub.2Si R'P,
R'.sub.2GeR'N, R'.sub.2Ge R'P, where R' is independently, a radical
group which is hydride, hydrocarbyl, substituted hydrocarbyl,
halocarbyl, substituted halocarbyl, hydrocarbyl-substituted
organometalloid, halocarbyl-substituted organometalloid,
disubstituted boron, disubstituted pnictogen, substituted
chalcogen, or halogen or two or more R' may be joined to form a
ring or ring system; and independently, each Q can be the same or
different is a hydride, substituted or unsubstituted, linear,
cyclic or branched, hydrocarbyl having from 1 to 30 carbon atoms,
halogen, alkoxides, aryloxides, amides, phosphides, or any other
univalent anionic ligand or combination thereof; also, two Q's
together may form an alkylidene ligand or cyclometallated
hydrocarbyl ligand or other divalent anionic chelating ligand,
where g is an integer corresponding to the formal oxidation state
of M, and d is an integer selected from 0, 1, 2, 3 or 4 and
denoting the degree of substitution, x is an integer from 0 to
1.
[0047] In one embodiment, the bulky ligand metallocene-type
catalyst compounds are those where the R substituents on the bulky
ligands L.sup.A, L.sup.B, (C.sub.5H.sub.4-dR.sub.d) of formulas (I)
and (II) are substituted with the same or different number of
substituents on each of the bulky ligands. In another embodiment,
the bulky ligands L.sup.A, L.sup.B, (C.sub.5H.sub.4-dR.sub.d) of
formulas (I) and (II) are different from each other.
[0048] Other bulky ligand metallocene-type catalysts compounds
useful in the invention include bridged heteroatom, mono-bulky
ligand metallocene-type compounds. These types of catalysts and
catalyst systems are described in, for example, PCT publication WO
92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO96/00244 and WO
97/15602 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438,
5,198,401, 5,227,440 and 5,264,405 and European publication EP-A-0
420 436, all of which are herein fully incorporated by reference.
Other bulky ligand metallocene-type catalyst compounds and catalyst
systems useful in the invention may include those described in U.S.
Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,
5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,
5,723,398 and 5,753,578 and PCT publications WO 93/08221, WO
93/08199, WO 95/07140, WO 98/11144 and European publications EP-A-0
578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0
839 834 and EP-B1-0 632 819, all of which are herein fully
incorporated by reference.
[0049] In another embodiment, the bulky ligand metallocene-type
catalyst compound is represented by the formula:
L.sup.CAJMQ.sub.n (III)
[0050] where M is a Group 3 to 16 metal atom or a metal selected
from the Group of actinides and lanthamides of the Periodic Table
of Elements, preferably M is a Group 4 to 12 transition metal, and
more preferably M is a Group 4, 5 or 6 transition metal, and most
preferably M is a Group 4 transition metal in any oxidation state,
especially titanium; Lc is a substituted or unsubstituted bulky
ligand bonded to M; J is bonded to M; A is bonded to M and J; J is
a heteroatom ancillary ligand; and A is a bridging group; Q is a
univalent anionic ligand; and n is the integer 0, 1 or 2. In
formula (III) above, L.sup.C, A and J form a fused ring system. In
an embodiment, L.sup.C of formula (III) is as defined above for
L.sup.A in formula (I), and A, M and Q of formula (III) are as
defined above in formula (I).
[0051] In another embodiment of this invention the bulky ligand
metallocene-type catalyst compound useful in the invention is
represented by the formula:
(C.sub.5H.sub.5-y-xR.sub.x)(A.sub.y)(JR'.sub.z-1-y)M(O).sub.n(L').sub.w
(IV)
[0052] where M is a transition metal from Group 4 in any oxidation
state, preferably, titanium, zirconium or hafnium, most preferably
titanium in either a +2, +3 or +4 oxidation state. A combination of
compounds represented by formula (IV) with the transition metal in
different oxidation states is also contemplated. L.sup.C is
represented by (C.sub.5H.sub.5-y-xR.sub.x) and is a bulky ligand as
described above. More particularly (C.sub.5H.sub.5-y-xR.sub.x) is a
cyclopentadienyl ring or cyclopentadienyl-type ring or ring system
which is substituted with from 0 to 5 substituent groups R, and "x"
is 0, 1, 2, 3 or 4 denoting the degree of substitution. Each R is,
independently, a radical selected from a group consisting of 1 to
30 non-hydrogen atoms. More particularly, R is a hydrocarbyl
radical or a substituted hydrocarbyl radical having from 1 to 30
carbon atoms, or a hydrocarbyl-substituted metalloid radical where
the metalloid is a Group 14 or 15 element, preferably silicon or
nitrogen or a combination thereof, and halogen radicals and
mixtures thereof. Substituent R groups also include silyl, germyl,
amine, and hydrocarbyloxy groups and mixtures thereof. Also, in
another embodiment, (C.sub.5H.sub.5-y-xR.sub.x) is a
cyclopentadienyl ligand in which two R groups, preferably two
adjacent R groups are joined to form a ring or ring system having
from 3 to 50 atoms, preferably from 3 to 30 carbon atoms. This ring
system may form a saturated or unsaturated polycyclic
cyclopentadienyl-type ligand such as those bulky ligands described
above, for example, indenyl, tetrahydroindenyl, fluorenyl or
octahydrofluorenyl.
[0053] The (JR'.sub.z-1-y) of formula (IV) is a heteroatom
containing ligand in which J is an element with a coordination
number of three from Group 15 or an element with a coordination
number of two from Group 16 of the Periodic Table of Elements.
Preferably J is a nitrogen, phosphorus, oxygen or sulfur atom with
nitrogen being most preferred. Each R' is, independently, a radical
selected from the group consisting of hydrocarbyl radicals having
from 1 to 20 carbon atoms, or as defined for R in formula (I)
above. The "y" is 0 or 1, and the "z" is the coordination number of
the element J. In one embodiment, in formula (IV), the J of formula
(III) is represented by (JR'.sub.z-1-y).
[0054] In formula (IV) each Q is, independently, any univalent
anionic ligand such as halogen, hydride, or substituted or
unsubstituted hydrpcarbyl having from 1 to 30 carbon atoms,
alkoxide, aryloxide, sulfide, silyl, amide or phosphide. Q may also
include hydrocarbyl groups having ethylenic unsaturation thereby
forming a .eta..sup.3 bond to M. Also, two Q's may be an
alkylidene, a cyclometallated hydrocarbyl or any other divalent
anionic chelating ligand. The integer n may be 0, 1, 2 or 3.
[0055] The A of formula (IV) is a covalent bridging group
containing a Group 13 to 16 element, preferably a Group 14 and 15
element, most preferably a Group 14 element. Non-limiting examples
of bridging group A include a dialkyl, alkylaryl or diaryl silicon
or germanium radical, alkyl or aryl phosphine or amine radical, or
a hydrocarbyl radical such as methylene, ethylene and the like.
[0056] Optionally associated with formula (IV) is L', a Lewis base
such as diethylether, tetraethylammonium chloride, tetrahydrofuran,
dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the
like; and w is a number from 0 to 3. Additionally, L' may be bonded
to any of R, R' or Q and n is 0, 1, 2 or 3.
[0057] In another embodiment, the bulky ligand type
metallocene-type catalyst compound is a complex of a metal,
preferably a transition metal, a bulky ligand, preferably a
substituted or unsubstituted pi-bonded ligand, and one or more
heteroallyl moieties, such as those described in U.S. Pat. Nos.
5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which are
herein fully incorporated by reference.
[0058] In an embodiment, the bulky ligand metallocene-type catalyst
compound is represented by the formula:
L.sup.DMQ.sub.2(YZ)A.sub.n (V)
[0059] where M is a Group 3 to 16 metal, preferably a Group 4 to 12
transition metal, and most preferably a Group 4, 5 or 6 transition
metal; L.sup.D is a substituted or unsubstituted bulky ligand that
is bonded to M; each Q is independently bonded to M and Q.sub.2(YZ)
forms a unicharged polydentate ligand; A or Q is a univalent
anionic ligand also bonded to M; n is 1 or 2.
[0060] In another embodiment, M is a Group 4, 5 or 6 transition
metal, preferably from Group 4, more preferably titanium, zirconium
and hafnium, and most preferably zirconium; L.sup.D is selected
from the group of bulky ligands consisting of cyclopentadienyl,
indenyl, tetrahydroindenyl, benzindenyl, fluorenyl,
octahydrofluorenyl, cyclooctatetraendiyl and including those bulky
ligands described above for L.sup.A of formula (1); Q is selected
from the group consisting of --O--, --NR--, --CR2-- and --S--; Y is
either C or S; Z is selected from the group consisting of --OR,
--NR.sub.2, --CR.sub.3, --SR, --SiR.sub.3, --PR.sub.2, --H, and
substituted or unsubstituted aryl groups, with the proviso that
when Q is --NR-- then Z is selected from one of the group
consisting of --OR, --NR.sub.2, --SR, --SiR.sub.3, --PR.sub.2 and
--H; R is selected from a group containing carbon, silicon,
nitrogen, oxygen, and/or phosphorus, preferably where R is a
hydrocarbon group containing from 1 to 20 carbon atoms, most
preferably an alkyl, cycloalkyl, or an aryl group; n is an integer
from 1 to 4, preferably 1 or 2; A is a univalent anionic group when
n is 2 or A is a divalent anionic group when n is 1; preferably A
is a carbamate, carboxylate, or other heteroallyl moiety described
by the Q, Y and Z combination. In another embodiment of formula
(V), optionally, T.sub.m is a bridging group bonded to L.sup.D and
another L.sup.D of another LDMQ.sub.2YZA.sub.n compound, where m is
an integer from 2 to 7, preferably 2 to 6, most preferably 2 or 3;
and T is selected from the group consisting of alkylene and arylene
groups containing from 1 to 10 carbon atoms optionally substituted
with carbon or heteroatoM(s), germanium, silicon and alkyl
phosphine.
[0061] In another embodiment of the invention, the bulky ligand
metallocene-type catalyst compounds are heterocyclic ligand
complexes where the bulky ligands, the ring(s) or ring systeM(s),
include one or more heteroatoms or a combination thereof.
Non-limiting examples of heteroatoms include a Group 13 to 16
element, preferably nitrogen, boron, sulfur, oxygen, aluminum,
silicon, phosphorous and tin. Examples of these bulky ligand
metallocene-type catalyst compounds are described in WO 96/33202,
WO 96/34021, WO 97/17379 and WO 98/22486 and U.S. Pat. Nos.
5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049 and
5,744,417, all of which are herein incorporated by reference.
[0062] In another embodiment, the bulky ligand metallocene-type
catalyst compounds are those complexes known as transition metal
catalysts based on bidentate ligands containing pyridine or
quinoline moieties, such as those described in U.S. application
Ser. No. 09/103,620 filed Jun. 23, 1998, which is herein
incorporated by reference.
[0063] In one embodiment, the bulky ligand metallocene-type
catalyst compound is represented by the formula:
((Z)XA.sub.t(YJ)).sub.qMQ.sub.n (VI)
[0064] where M is a metal selected from Group 3 to 13 or lanthamide
and actinide series of the Periodic Table of Elements; Q is bonded
to M and each Q is a monovalent, bivalent, or trivalent anion; X
and Y are bonded to M; one or more of X and Y are heteroatoms,
preferably both X and Y are heteroatoms; Y is contained in a
heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen
atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Z
comprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon
atoms, preferably Z is a cyclic group containing 3 to 50 atoms,
preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a
bridging group joined to at least one of X,Y or J, preferably X and
J; q is 1 or 2; n is an integer from 1 to 4 depending on the
oxidation state of M. In one embodiment, where X is oxygen or
sulfur then Z is optional. In another embodiment, where X is
nitrogen or phosphorous then Z is present. In an embodiment, Z is
preferably an aryl group, more preferably a substituted aryl
group.
[0065] In another embodiment, these metallocene-type catalyst
compounds are represented by the formula:
((R'.sub.mZ)XA.sub.t(YJR".sub.m)).sub.qMQ.sub.n (VII)
[0066] where M is a metal selected from Group 3 to 13 of the
Periodic Table of Elements, preferably a Group 4 to 12 transition
metal, more preferably a Group 4, 5 or 6 transition metal, even
more preferably a Group 4 transition metal such as titanium,
zirconium or hafnium, and most preferably zirconium;
[0067] Each Q is bonded to M and each Q is a monovalent, bivalent,
or trivalent anion. Preferably each Q is independently selected
from the group consisting of halogens, hydrogen, alkyl, aryl,
alkenyl, alkylaryl, arylalkyl, hydrocarboxy or phenoxy radicals
having 1-20 carbon atoms. Each Q may also be amides, phosphides,
sulfides, silylalkyls, diketonates, and carboxylates. Optionally,
each Q may contain one or more heteroatoms, more preferably each Q
is selected from the group consisting of halides, alkyl radicals
and arylalkyl radicals. Most preferably, each Q is selected from
the group consisting of arylalkyl radicals such as benzyl.
[0068] X and Y are preferably each heteroatoms, more preferably
independently selected from the group consisting of nitrogen,
oxygen, sulfur and phosphorous, even more preferably nitrogen or
phosphorous, and most preferably nitrogen;
[0069] Y is contained in a heterocyclic ring or ring system J. J
contains from 2 to 30 carbon atoms, preferably from 2 to 7 carbon
atoms, more preferably from 3 to 6 carbon atoms, and most
preferably 5 carbon atoms. Optionally, the heterocyclic ring J
containing Y, may contain additional heteroatoms. J may be
substituted with R" groups that are independently selected from the
group consisting of hydrogen or linear, branched, cyclic, alkyl
radicals, or alkenyl, alkynl, alkoxy, aryl or aryloxy radicals.
Also, two or more R" groups may be joined to form a cyclic moiety
such as an aliphatic or aromatic ring. Preferably R" is hydrogen or
an aryl group, most preferably R"8 is hydrogen. When R" is an aryl
group and Y is nitrogen, a quinoline group is formed. Optionally,
an R" may be joined to A;
[0070] Z is a hydrocarbyl group bonded to X, preferably Z is a
hydrocarbyl group of from 1 to 50 carbon atoms, preferably Z is a
cyclic group having from 3 to 30 carbon atoms, preferably Z is a
substituted or unsubstituted cyclic group containing from 3 to 30
carbon atoms, optionally including one or more heteroatoms, more
preferably Z is an aryl group, most preferably a substituted aryl
group;
[0071] Z may be substituted with R' groups that are independently
selected from group consisting of hydrogen or linear, branched,
alkyl radicals or cyclic alkyl, alkenyl, alkynl or aryl radicals.
Also, two or more R' groups may be joined to form a cyclic moiety
such as an aliphatic or aromatic ring. Preferably R' is an alkyl
group having from 1 to 20 carbon atoms, more preferably R' is
methyl, ethyl, propyl, butyl, pentyl and the like, including
isomers thereof, more preferably R' is a secondary or tertiary
hydrocarbon, including isopropyl, t-butyl and the like, most
preferably R' is an isopropyl group. Optionally, an R' group may be
joined to A. It is preferred that at least one R' is ortho to
X;
[0072] When t is 1, A is a bridging group joined to at least one
of, preferably both of, X and J. Bridging group A contains one or
more Group 13 to 16 elements from Periodic Table of Elements. More
preferably A contains one or more Group 14 elements, most
preferably A is a substituted carbon group, a di-substituted carbon
group or vinyl group; and
[0073] In formula (VII) m is independently an integer from 0 to 5,
preferably 2; n is an integer from 1 to 4 and typically depends on
the oxidation state of M; and q is 1 or 2, and where q is 2, the
two ((R'.sub.mZ)XA(YJR".sub.m)) of formula (VII) are bridged to
each other via a bridging group, preferably a bridging group
containing a Group 14 element. Also, in a preferred embodiment, the
compound represented by formula (VI) or (VII) may be contacted with
acetone.
[0074] Other Bulky Ligand Metallocene-Type Catalyst Compounds
[0075] It is within the scope of this invention, in one embodiment,
that the bulky ligand metallocene-type catalyst compounds include
complexes of Ni.sup.2+ and Pd.sup.2+ described in the articles
Johnson, et al., "New Pd(II)- and Ni(II)-Based Catalysts for
Polymerization of Ethylene and a-Olefins", J. Am. Chem. Soc. 1995,
117, 6414-6415 and Johnson, et al., "Copolymerization of Ethylene
and Propylene with Functionalized Vinyl Monomers by PalladiuM(II)
Catalysts", J. Am. Chem. Soc., 1996, 118, 267-268, and WO 96/23010
published Aug. 1, 1996, which are all herein fully incorporated by
reference. These complexes can be either dialkyl ether adducts, or
alkylated reaction products of the described dihalide complexes
that can be activated to a cationic state by the activators of this
invention described below.
[0076] Also included as bulky ligand metallocene-type catalyst are
those diimine based ligands of Group 8 to 10 metal compounds
disclosed in PCT publications WO 96/23010 and WO 97/48735 and
Gibson, et. al., Chem. Comm., pp. 849-850 (1998), all of which are
herein incorporated by reference.
[0077] Other bulky ligand metallocene-type catalysts are those
Group 5 and 6-metal imido complexes described in EP-A2-0 816 384,
which is incorporated herein by reference. In addition, bulky
ligand metallocene-type catalysts include bridged bis(arylamido)
Group 4 compounds described by D. H. McConville, et al., in
Organometallics 1195, 14, 5478-5480, which is herein incorporated
by reference.
[0078] It is also contemplated that in one embodiment, the bulky
ligand metallocene-type catalysts of the invention described above
include their structural or optical or enantiomeric isomers (meso
and racemic isomers) and mixtures thereof.
[0079] Activator and Activation Methods for the Bulky Ligand
Metallocene-Type Catalyst Compounds
[0080] The above described bulky ligand metallocene-type catalyst
compounds having a least one fluoride leaving group or a fluorine
containing leaving group are typically activated in various ways to
yield catalyst compounds having a vacant coordination site that
will coordinate, insert, and polymerize olefin(s).
[0081] For the purposes of this patent specification and appended
claims, the term "activator" is defined to be any compound or
component or method which can activate any of the bulky ligand
metallocene-type catalyst compounds of the invention as described
above. Non-limiting activators, for example may include a Lewis
acid or a non-coordinating ionic activator or ionizing activator or
any other compound including Lewis bases, aluminum alkyls,
conventional-type cocatalysts and combinations thereof that can
convert a neutral bulky ligand metallocene-type catalyst compound
to a catalytically active bulky ligand metallocene cation. It is
within the scope of this invention to use alumoxane or modified
alumoxane as an activator, and/or to also use ionizing activators,
neutral or ionic, such as tri (n-butyl) ammonium tetrakis
(pentafluorophenyl) boron or a trisperfluorophenyl boron metalloid
precursor that would ionize the neutral bulky ligand
metallocene-type catalyst compound.
[0082] In one embodiment, an activation method using ionizing ionic
compounds not containing an active proton but capable of producing
both a bulky ligand metallocene-type catalyst cation and a
non-coordinating anion are also contemplated, and are described in
EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568, which
are all herein incorporated by reference.
[0083] There are a variety of methods for preparing alumoxane and
modified alumoxanes, non-limiting examples of which are described
in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199,
5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,
5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793,
5,391,529, 5,693,838, 5,731,253, 5,731,451 5,744,656 and European
publications EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218,
and PCT publication WO 94/10180, all of which are herein fully
incorporated by reference.
[0084] Ionizing compounds may contain an active proton, or some
other cation associated with but not coordinated to or only loosely
coordinated to the remaining ion of the ionizing compound. Such
compounds and the like are described in European publications
EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-500 944,
EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,
5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124
and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,
1994, all of which are herein fully incorporated by reference.
[0085] Other activators include those described in PCT publication
WO 98/07515 such as tris (2,2',2"-nonafluorobiphenyl)
fluoroaluminate, which publication is fully incorporated herein by
reference. Combinations of activators are also contemplated by the
invention, for example, alumoxanes and ionizing activators in
combinations, see for example, PCT publications WO 94/07928 and WO
95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which
are herein fully incorporated by reference. WO 98/09996
incorporated herein by reference describes activating bulky ligand
metallocene-type catalyst compounds with perchlorates, periodates
and iodates including their hydrates. WO 98/30602 and WO 98/30603
incorporated by reference describe the use of lithium
(2,2'-bisphenyl-ditrimethylsilicate).4THF as an activator for a
bulky ligand metallocene-type catalyst compound. Also, methods of
activation such as using radiation (see EP-B1-0 615 981 herein
incorporated by reference), electro-chemical oxidation, and the
like are also contemplated as activating methods for the purposes
of rendering the neutral bulky ligand metallocene-type catalyst
compound or precursor to a bulky ligand metallocene-type cation
capable of polymerizing olefins.
[0086] It is also within the scope of this invention that the above
described bulky ligand metallocene-type catalyst compounds can be
combined with one or more of the catalyst compounds represented by
formulas (I) through (VII) with one or more activators or
activation methods described above.
[0087] It is further contemplated by the invention that other
catalysts can be combined with the bulky ligand metallocene-type
catalyst compounds of the invention. For example, see U.S. Pat.
Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and
5,719,241 all of which are herein fully incorporated herein
reference. It is also contemplated that any one of the bulky ligand
metallocene-type catalyst compounds of the invention having at
least one fluoride or fluorine containing leaving group as
described in U.S. application Ser. No. 09/191,916 filed Nov. 13,
1998.
[0088] In another embodiment of the invention one or more bulky
ligand metallocene-type catalyst compounds or catalyst systems may
be used in combination with one or more conventional-type catalyst
compounds or catalyst systems. Non-limiting examples of mixed
catalysts and catalyst systems are described in U.S. Pat. Nos.
4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867,
5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCT
Publication WO 96/23010 published Aug. 1, 1996, all of which are
herein fully incorporated by reference.
[0089] Method for Supporting
[0090] The above described bulky ligand metallocene-type catalyst
compounds and catalyst systems may be combined with one or more
support materials or carriers using one of the support methods well
known in the art or as described below. In the preferred
embodiment, the method of the invention uses a polymerization
catalyst in a supported form. For example, in a most preferred
embodiment, a bulky ligand metallocene-type catalyst compound or
catalyst system is in a supported form, for example deposited on,
contacted with, or incorporated within, adsorbed or absorbed in, or
on, a support or carrier.
[0091] The terms "support" or "carrier" are used interchangeably
and are any support material, preferably a porous support material,
for example, talc, inorganic oxides and inorganic chlorides. Other
carriers include resinous support materials such as polystyrene,
functionalized or crosslinked organic supports, such as polystyrene
divinyl benzene polyolefins or polymeric compounds, zeolites,
clays, or any other organic or inorganic support material and the
like, or mixtures thereof.
[0092] The preferred carriers are inorganic oxides that include
those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred
supports include silica, alumina, silica-alumina, magnesium
chloride, and mixtures thereof. Other useful supports include
magnesia, titania, zirconia, montmorillonite (EP-B1 0 511 665) and
the like. Also, combinations of these support materials may be
used, for example, silica-chromium, silica-alumina, silica-titania
and the like.
[0093] It is preferred that the carrier, most preferably an
inorganic oxide, has a surface area in the range of from about 10
to about 700 m.sup.2/g, pore volume in the range of from about 0.1
to about 4.0 cc/g and average particle size in the range of from
about 5 to about 500 .mu.m. More preferably, the surface area of
the carrier is in the range of from about 50 to about 500
m.sup.2/g, pore volume of from about 0.5 to about 3.5 cc/g and
average particle size of from about 10 to about 200 .mu.m. Most
preferably the surface area of the carrier is in the range is from
about 100 to about 400 m.sup.2/g, pore volume from about 0.8 to
about 3.0 cc/g and average particle size is from about 5 to about
100 .mu.m. The average pore size of the carrier of the invention
typically has pore size in the range of from 10 to 1000 .ANG.,
preferably 50 to about 500 .ANG., and most preferably 75 to about
350 .ANG..
[0094] Examples of supporting the bulky ligand metallocene-type
catalyst systems of the invention are described in U.S. Pat. Nos.
4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228,
5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649,
5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,
5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400,
5,723,402, 5,731,261, 5,759,940, 5,767,032 and 5,770,664 and U.S.
Application Serial Nos. 271,598 filed Jul. 7, 1994 and 788,736
filed Jan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044,
WO 96/06187 and WO 97/02297 all of which are herein fully
incorporated by reference.
[0095] In one embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention may be deposited on the same or
separate supports together with an activator, or the activator may
be used in an unsupported form, or may be deposited on a support
different from the supported bulky ligand metallocene-type catalyst
compounds of the invention, or any combination thereof.
[0096] There are various other methods in the art for supporting a
polymerization catalyst compound or catalyst system of the
invention. For example, the bulky ligand metallocene-type catalyst
compound of the invention may contain a polymer bound ligand as
described in U.S. Pat. Nos. 5,473,202 and 5,770,755, which is
herein fully incorporated by reference; the bulky ligand
metallocene-type catalyst system of the invention may be spray
dried as described in U.S. Pat. No. 5,648,310, which is herein
fully incorporated by reference; the support used with the bulky
ligand metallocene-type catalyst system of the invention is
functionalized as described in European publication EP-A-0 802 203,
which is herein fully incorporated by reference, or at least one
substituent or leaving group is selected as described in U.S. Pat.
No. 5,688,880, which is herein fully incorporated by reference.
[0097] In a preferred embodiment, the invention provides for a
supported bulky ligand metallocene-type catalyst system that
includes an antistatic agent or surface modifier that is used in
the preparation of the supported catalyst system as described in
PCT publication WO 96/11960, which is herein fully incorporated by
reference. The catalyst systems of the invention can be prepared in
the presence of an olefin, for example hexene-1.
[0098] A preferred method for producing the supported bulky ligand
metallocene-type catalyst system of the invention is described
below and is described in U.S. application Ser. No. 265,533, filed
Jun. 24, 1994 and Ser. No. 265,532, filed Jun. 24, 1994 and PCT
publications WO 96/00245 and WO 96/00243 both published Jan. 4,
1996, all of which are herein fully incorporated by reference. In
this preferred method, the bulky ligand metallocene-type catalyst
compound is slurried in a liquid to form a metallocene solution and
a separate solution is formed containing an activator and a liquid.
The liquid may be any compatible solvent or other liquid capable of
forming a solution or the like with the bulky ligand
metallocene-type catalyst compounds and/or activator of the
invention. In the most preferred embodiment the liquid is a cyclic
aliphatic or aromatic hydrocarbon, most preferably toluene. The
bulky ligand metallocene-type catalyst compound and activator
solutions are mixed together and added to a porous support or the
porous support is added to the solutions such that the total volume
of the bulky ligand metallocene-type catalyst compound solution and
the activator solution or the bulky ligand metallocene-type
catalyst compound and activator solution is less than four times
the pore volume of the porous support, more preferably less than
three times, even more preferably less than two times; preferred
ranges being from 1.1 times to 3.5 times range and most preferably
in the 1.2 to 3 times range.
[0099] Procedures for measuring the total pore volume of a porous
support are well known in the art. Details of one of these
procedures is discussed in Volume 1, Experimental Methods in
Catalytic Research (Academic Press, 1968) (specifically see pages
67-96). This preferred procedure involves the use of a classical
BET apparatus for nitrogen absorption. Another method well known in
the art is described in Innes, Total Porosity and Particle Density
ofFluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical
Chemistry 332-334 (March, 1956).
[0100] The mole ratio of the metal of the activator component to
the metal of the supported bulky ligand metallocene-type catalyst
compounds are in the range of between 0.3:1 to 1000:1, preferably
20:1 to 800:1, and most preferably 50:1 to 500:1. Where the
activator is an ionizing activator such as those based on the anion
tetrakis(pentafluorophenyl)boron, the mole ratio of the metal of
the activator component to the metal component of the bulky ligand
metallocene-type catalyst is preferably in the range of between
0.3:1 to 3:1. Where an unsupported bulky ligand metallocene-type
catalyst system is utilized, the mole ratio of the metal of the
activator component to the metal of the bulky ligand
metallocene-type catalyst compound is in the range of between 0.3:1
to 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1
to 2000:1.
[0101] In one embodiment of the invention, olefin(s), preferably
C.sub.2 to C.sub.30 olefin(s) or alpha-olefin(s), preferably
ethylene or propylene or combinations thereof are prepolymerized in
the presence of the bulky ligand metallocene-type catalyst system
of the invention prior to the main polymerization. The
prepolymerization can be carried out batchwise or continuously in
gas, solution or slurry phase including at elevated pressures. The
prepolymerization can take place with any olefin monomer or
combination and/or in the presence of any molecular weight
controlling agent such as hydrogen. For examples of
prepolymerization procedures, see U.S. Pat. Nos. 4,748,221,
4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and
European publication EP-B-0279 863 and PCT Publication WO 97/44371
all of which are herein fully incorporated by reference.
[0102] In one embodiment the polymerization catalyst is used in an
unsupported form, preferably in a liquid form such as described in
U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication
EP-A-0 593 083, all of which are herein incorporated by reference.
The polymerization catalyst in liquid form can be fed to a reactor
as described in PCT publication WO 97/46599, which is fully
incorporated herein by reference.
[0103] Organic Polyhydroxyl Compounds
[0104] Organic polyhydroxyl compounds are well known in the art.
For the purposes of this patent specification and appended claims
an organic polyhydroxyl compound of the invention is represented by
the general formula:
R(R'R"C--OH).sub.3+x (A)
[0105] where x is greater than 0, preferably greater than 1, most
preferably equal to or greater 2, R has from 1 to 1000 non-hydrogen
atoms, preferably 1 to 500 carbon atoms, more preferably from 1 to
100 carbon atoms, and R' and R", independently can be hydrogen or
from 1 to 1000 non-hydrogen atoms, preferably 1 to 500 carbon
atoms, more preferably from 1 to 100 carbon atoms. R' and R" can be
the same or different. Each R, R' and/or R" may be optionally
substituted with heteroatoms or other substituents. The R, R'and/or
R" may be branched or unbranched, saturated or unsaturated
aliphatic or cycloaliphatic groups or aromatic groups or mixtures
of aliphatic or aromatic groups. In one embodiment, the organic
polyhydroxyl compound of formula (A) does not include the R". In
another embodiment, in the organic polyhydroxyl compound of formula
(A), R" is hydrogen.
[0106] In a preferred embodiment of the invention the organic
polyhydroxyl compounds have three or more adjacent hydroxyl
groups.
[0107] In another preferred embodiment, of formula (A) above x is 0
to 1000, preferably x is 1 to 500, most preferably 2 to 250.
[0108] In one preferred embodiment of the invention, R" is hydrogen
and preferably x is 2.
[0109] The preferred organic polyhydroxyl compounds are sugar
derived compounds, for example glycerol, glucose, xylose, xylitol,
sucrose, and cellulose, the most preferred organic polyhydroxyl
compound being xylitol.
[0110] Non-limiting examples of organic polyhydroxyl compounds
include, but are not limited to, arabinogalactan; butanetriol;
alpha-acetoxyphenyl-acetonitrile; butanetriol;
1,1,1,5,5,5-hexafluoro-2,2- ,4,4-pentane-tetrol;
1,1,1-tris(hydroxymethyl)ethane; 1,2,3-heptanetriol;
1,2,3-trihydroxyhexane; 1,2,4-butanetriol; 1,2,6-trihydroxyhexane;
1,2-O-isopropylidene-D-glucofuranose;
1,2:3,4-di-O-isopropylidene-D-galac- to-pyranose;
1,6-anhydro-beta-D-glucose; 1-O-octyl-beta-D-glucopyranoside;
1-S-octyl-beta-D-thioglucopyranoside;
2,3:5,6-di-O-isopropylidene-alpha-D- -mannofuranose;
2,5-O-methylene-D-mannitol; 2-(bromomethyl)-2-(hydroxymeth-
yl)-1,3-propanediol; 2-(hydroxymethyl)-1,3-propanediol;
2-chloroethyl-beta-D-fructopyranoside; 2-deoxy-D-galactose;
2-deoxy-D-glucose; 2-deoxy-D-ribose; 2-fluoro-2-deoxy-D-glucose;
3,7,11,15-tetramethyl-1,2,3-hexa-decanetriol;
3-fluoro-3-deoxy-D-glucose; 3-methyl-1,3,5-pentanetriol;
3-O-methylgucose; 4,6-O-ethylidene-alpha-D-g- lucose;
5-thio-D-glucose; acacia; adonitol; agar; agarose;
alpha-chloralose; alpha-cyclodextrin Hydrate; alpha-D-talose;
alpha-D-glucose; alpha-D-lactose monohydrate; alpha-D-melibiose
hydrate; alpha-methyl-D-mannopyranoside; amylose; beta-chloralose;
beta-cyclodextrin hydrate; beta-cyclodextrin; beta-D-lactose;
tagatose; D-allose; D-altrose; D-arabinose; D-arabitol;
maltopentaose hydrate; maltotetraose; maltotriose hydrate;
maltulose monohydrate; melezitose hydrate; meso-erythritol;
methyl-alpha-D-glucopyranoside; methyl-beta-cyclodextrin;
methyl-beta-D-arabinopyranoside; methyl-beta-D-galactopyranoside;
methyl-beta-D-glucopyranoside hemihyrate;
methyl-beta-D-xylopyranoside; palatinose hydrate; pentaerythritol;
sorbitol; stachyose tetrahydrate; starch; sucrose;
trimethylolpropane; xylan; xylitol; D-cellobiose; D-erythrose;
D-fructose; D-fucose; D-galactose, all of which are available from
Aldrich, Milwaukee, Wis.
[0111] In one embodiment the organic polyhydroxyl compound of the
invention has a melting pint above 50.degree. C., most preferably
above 80.degree. C.
[0112] In an embodiment of the invention, more than one organic
polyhydroxyl compound is utilized.
[0113] The organic polyhydroxyl compound in one embodiment may be
combined with antistatic agents such as fatty amines, for example,
Kemamine AS 990/2 zinc additive, a blend of ethoxylated stearyl
amine and zinc stearate, or Kemamine AS 990/3, a blend of
ethoxylated stearyl amine, zinc stearate and
octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Both these
blends are available from Witco Corporation, Memphis, Term. In
another embodiment, the organic polyhydroxyl compound can be
combined with a carboxylic acid salt of a metal ester, for example
aluminum carboxylates such as aluminum mono, di- and tri-stearates,
aluminum octoates, oleates and cyclohexylbutyrates, as described in
U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998. In yet
another embodiment, the organic polyhydroxyl compound of the
invention may be used in combination with a carbonyl compound such
as benzil.
[0114] Method of Preparing the Catalyst Composition
[0115] The method for making the catalyst composition generally
involves the combining, contacting, blending, and/or mixing of a
catalyst system or polymerization catalyst with a organic
polyhydroxyl compound.
[0116] In one embodiment of the method of the invention, a
conventional-type transition metal catalyst and/or a bulky ligand
metallocene-type catalyst is combined, contacted, blended, and/or
mixed with at least one organic polyhydroxyl compound. In a most
preferred embodiment, the conventional-type transition metal
catalyst and/or the bulky ligand metallocene-type catalyst are
supported on a carrier.
[0117] In another embodiment, the steps of the method of the
invention include forming a polymerization catalyst, preferably
forming a supported polymerization catalyst, and contacting the
polymerization catalyst with at least one organic polyhydroxyl
compound. In a preferred method, the polymerization catalyst
comprises a catalyst compound, an activator or cocatalyst and a
carrier, preferably the polymerization catalyst is a supported
bulky ligand metallocene-type catalyst.
[0118] One in the art recognizes that depending on the catalyst
system and the organic polyhydroxyl compound used certain
conditions of temperature and pressure would be required to
prevent, for example, a loss in the activity of the catalyst
system.
[0119] In one embodiment of the method of the invention the organic
polyhydroxyl compound is contacted with the catalyst system,
preferably a supported catalyst system, most preferably a supported
bulky ligand metallocene-type catalyst system under ambient
temperatures and pressures. Preferably the contact temperature for
combining the polymerization catalyst and the organic polyhydroxyl
compound is in the range of from 0.degree. C. to about 100.degree.
C., more preferably from 15.degree. C. to about 75.degree. C., most
preferably at about ambient temperature and pressure.
[0120] In a preferred embodiment, the contacting of the
polymerization catalyst and the organic polyhydroxyl compound is
performed under an inert gaseous atmosphere, such as nitrogen.
However, it is contemplated that the combination of the
polymerization catalyst and the organic polyhydroxyl compound may
be performed in the presence of olefin(s), solvents, hydrogen and
the like.
[0121] In one embodiment, the organic polyhydroxyl compound may be
added at any stage during the preparation of the polymerization
catalyst.
[0122] In one embodiment of the method of the invention, the
polymerization catalyst and the organic polyhydroxyl compound are
combined in the presence of a liquid, for example the liquid may be
a mineral oil, toluene, hexane, isobutane or a mixture thereof. In
a more preferred method the organic polyhydroxyl compound is
combined with a polymerization catalyst that has been formed in a
liquid, preferably in a slurry, or combined with a substantially
dry or dried, polymerization catalyst that has been placed in a
liquid and reslurried.
[0123] In an embodiment, the contact time for the organic
polyhydroxyl compound and the polymerization catalyst may vary
depending on one or more of the conditions, temperature and
pressure, the type of mixing apparatus, the quantities of the
components to be combined, and even the mechanism for introducing
the polymerization catalyst/organic polyhydroxyl compound
combination into the reactor.
[0124] Preferably, the polymerization catalyst, preferably a bulky
ligand metallocene-type catalyst compound and a carrier, is
contacted with a organic polyhydroxyl compound for a period of time
greater than a second, preferably from about 1 minute to about 48
hours, more preferably from about 10 minutes to about 10 hours, and
most preferably from about 30 minutes to about 6 hours. The period
of contacting refers to the mixing time only.
[0125] In an embodiment, the ratio of the weight of the organic
polyhydroxyl compound to the weight of the transition metal of the
catalyst compound is in the range of from about 0.01 to about 1000
weight percent, preferably in the range of from 1 to about 100
weight percent, more preferably in the range of from about 2 to
about 50 weight percent, and most preferably in the range of from 4
to about 20 weight percent. In one embodiment, the ratio of the
weight of the organic polyhydroxyl compound to the weight of the
transition metal of the catalyst compound is in the range of from
about 2 to about 20, more preferably in the range of from about 2
to about 12, and most preferably in the range of from 4 to about
10.
[0126] In another embodiment of the method of the invention, the
weight percent of the organic polyhydroxyl compound based on the
total weight of the polymerization catalyst is in the range of from
about 0.5 weight percent to about 500 weight percent, preferably in
the range of from 1 weight percent to about 25 weight percent, more
preferably in the range of from about 2 weight percent to about 12
weight percent, and most preferably in the range of from about 2
weight percent to about 10 weight percent. In another embodiment,
the weight percent of the organic polyhydroxyl compound based on
the total weight of the polymerization catalyst is in the range of
from 1 to about 50 weight percent, preferably in the range of from
2 weight percent to about 30 weight percent, and most preferably in
the range of from about 2 weight percent to about 20 weight
percent.
[0127] Mixing techniques and equipment contemplated for use in the
method of the invention are well known. Mixing techniques may
involve any mechanical mixing means, for example shaking, stirring,
tumbling, and rolling. Another technique contemplated involves the
use of fluidization, for example in a fluid bed reactor vessel
where circulated gases provide the mixing. Non-limiting examples of
mixing equipment for combining, in the most preferred embodiment a
solid polymerization catalyst and a solid organic polyhydroxyl
compound, include a ribbon blender, a static mixer, a double cone
blender, a drum tumbler, a drum roller, a dehydrator, a fluidized
bed, a helical mixer and a conical screw mixer.
[0128] In an embodiment of the method of the invention, a supported
conventional-type transition metal catalyst, preferably a supported
bulky ligand metallocene-type catalyst, is tumbled with a organic
polyhydroxyl compound for a period of time such that a substantial
portion of the supported catalyst is intimately mixed and/or
substantially contacted with the organic polyhydroxyl compound.
[0129] In a preferred embodiment of the invention the catalyst
system of the invention is supported on a carrier, preferably the
supported catalyst system is substantially dried, preformed,
substantially dry and/or free flowing. In an especially preferred
method of the invention, the preformed supported catalyst system is
contacted with at least one organic polyhydroxyl compound. The
organic polyhydroxyl compound may be in solution or slurry or in a
dry state, preferably the organic polyhydroxyl compound is in a
substantially dry or dried state. In the most preferred embodiment,
the organic polyhydroxyl compound is contacted with a supported
catalyst system, preferably a supported bulky ligand
metallocene-type catalyst system in a rotary mixer under a nitrogen
atmosphere, most preferably the mixer is a tumble mixer, or in a
fluidized bed mixing process, in which the polymerization catalyst
and the organic polyhydroxyl compound are in a solid state, that is
they are both substantially in a dry state or in a dried state.
[0130] In an embodiment of the method of the invention a
conventional-type transition metal catalyst compound, preferably a
bulky ligand metallocene-type catalyst compound, is contacted with
a carrier to form a supported catalyst compound. In this method, an
activator or a cocatalyst for the catalyst compound is contacted
with a separate carrier to form a supported activator or supported
cocatalyst. It is contemplated in this particular embodiment of the
invention, that a organic polyhydroxyl compound is then mixed with
the supported catalyst compound or the supported activator or
cocatalyst, in any order, separately mixed, simultaneously mixed,
or mixed with only one of the supported catalyst, or preferably the
supported activator prior to mixing the separately supported
catalyst and activator or cocatalyst.
[0131] In another embodiment, the polymerization catalyst/organic
polyhydroxyl compound may be contacted with a liquid, such as
mineral oil and introduced to a polymerization process in a slurry
state. In this particular embodiment, it is preferred that the
polymerization catalyst is a supported polymerization catalyst.
[0132] In an embodiment, the method of the invention provides for
co-injecting an unsupported polymerization catalyst and a organic
polyhydroxyl compound into the reactor. In one embodiment the
polymerization catalyst is used in an unsupported form, preferably
in a liquid form such as described in U.S. Pat. Nos. 5,317,036 and
5,693,727 and European publication EP-A-0 593 083, all of which are
herein incorporated by reference. The polymerization catalyst in
liquid form can be fed with a organic polyhydroxyl compound to a
reactor using the injection methods described in PCT publication WO
97/46599, which is fully incorporated herein by reference.
[0133] Where a organic polyhydroxyl compound and an unsupported
bulky ligand metallocene-type catalyst system combination is
utilized, the mole ratio of the metal of the activator component to
the metal of the bulky ligand metallocene-type catalyst compound is
in the range of between 0.3:1 to 10,000:1, preferably 100:1 to
5000:1, and most preferably 500:1 to 2000:1.
[0134] In one embodiment, the polymerization catalyst and/or
catalyst composition, the polymerization catalyst and the organic
polyhydroxyl compound have a productivity greater than 1500 grams
of polymer per gram of catalyst, preferably greater than 2000 grams
of polymer per gram of catalyst, more preferably greater than 2500
grams of polymer per gram of catalyst and most preferably greater
than 3000 grams of polymer per gram of catalyst.
[0135] In another embodiment, the polymerization catalyst and/or
catalyst composition, the polymerization catalyst and the organic
polyhydroxyl compound, have a productivity greater than 2000 grams
of polymer per gram of catalyst, preferably greater than 3000 grams
of polymer per gram of catalyst, more preferably greater than 4000
grams of polymer per gram of catalyst and most preferably greater
than 5000 grams of polymer per gram of catalyst.
[0136] In one embodiment, the polymerization catalyst and/or the
catalyst composition has a reactivity ratio generally less than 2,
more typically less than 1. Reactivity ratio is defined to be the
mole ratio of comonomer to monomer entering the reactor, for
example as measured in the gas composition in a gas phase process,
divided by the mole ratio of the comonomer to monomer in the
polymer product being produced. In a preferred embodiment, the
reactivity ratio is less than 0.6, more preferably less than 0.4,
and most preferably less than 0.3. In the most preferred
embodiment, the monomer is ethylene and the comonomer is an olefin
having 3 or more carbon atoms, more preferably an alpha-olefin
having 4 or more carbon atoms, and most preferably an alpha-olefin
selected from the group consisting of butene-1,4-methyl-pentene-1,
pentene-1, hexene-1 and octene-1.
[0137] In another embodiment of the invention, when transitioning
from a first polymerization catalyst to a second polymerization
catalyst, preferably where the first and second polymerization
catalysts are bulky ligand metallocene-type catalyst compound, more
preferably where the second polymerization catalyst is a bridged,
bulky ligand metallocene-type catalyst compound, it would be
preferable during the transition to use a catalyst composition of a
organic polyhydroxyl compound combined with a bridged, bulky ligand
metallocene-type catalyst.
[0138] When starting up a polymerization process, especially a gas
phase process, there is a higher tendency for operability problems
to occur. Thus, it is contemplated in the present invention that a
polymerization catalyst and organic polyhydroxyl compound mixture
is used on start-up to reduce or eliminate start-up problems.
Furthermore, it also contemplated that once the reactor is
operating in a stable state, a transition to the same or a
different polymerization catalyst without the organic polyhydroxyl
compound can be made.
[0139] In another embodiment, during a polymerization process that
is or is about to be disrupted, a polymerization catalyst/organic
polyhydroxyl compound mixture of the invention could be
transitioned to. This switching of polymerization catalysts is
contemplated to occur when operability problems arise. Indications
of operability problems are well known in the art. Some of which in
a gas phase process include temperature excursions in the reactor,
unexpected pressure changes, excessive static generation or
unusually high static spikes, chunking, sheeting and the like. In
an embodiment, the organic polyhydroxyl compound may be added
directly to the reactor, particularly when operability problems
arise.
[0140] It is contemplated that using the polymerization catalyst
combined with a organic polyhydroxyl compound of the invention it
is easier to produce fractional melt index and higher density
polymers. In one embodiment, the invention provides for a process
for polymerizing olefin(s) in a reactor in the presence of a
polymerization catalyst in combination with a organic polyhydroxyl
compound to produce a polymer product having a melt index less than
about 1 dg/min and a density greater than 0.920 g/cc, more
preferably the polymer product has a melt index less than about
0.75 dg/min and a density greater than 0.925 g/cc. Preferably the
polymerization catalyst is a bulky ligand metallocene-type
catalyst, more preferably the process is a gas phase process and
the polymerization catalyst includes a carrier.
[0141] It is contemplated that using the combination polymerization
catalyst/organic polyhydroxyl compound of the invention,
transitioning to one of the more difficult grades of polymers would
be simpler. Thus, in one embodiment, the invention is directed to a
process for polymerizing olefin(s) in the presence of a first
catalyst composition, under steady state conditions, preferably gas
phase process conditions, to produce a first polymer product. The
first polymer product having a density greater than 0.87 g/cc,
preferably greater than 0.900 g/cc, more preferably greater than
0.910 g/cc, and a melt index in the range of from 1 dg/min to about
200 dg/min, preferably in the range of greater than 1 dg/min to
about 100 dg/min, more preferably from greater than 1 dg/min to
about 50 dg/min, most preferably from greater than 1 dg/min to
about 20 dg/min. This process further comprises the step of
transitioning to a second catalyst composition to produce second
polymer product having a density greater than 0.920 g/cc,
preferably greater than 0.925 g/cc, and a melt index less than 1
dg/min, preferably less than 0.75 dg/min. The second catalyst
composition comprising, in combination, a conventional-type
transition metal catalyst and/or a bulky ligand metallocene-type
catalyst, and a organic polyhydroxyl compound. It is also within
the scope of this particular embodiment to transition from a first
polymer product having an I.sub.21/I.sub.2 (described below) of
less than 25 to a second polymer product having an I.sub.21/I.sub.2
greater than 25, preferably greater than 30, and even more
preferably greater than 35.
[0142] In yet another embodiment, the process of the invention
involves alternating between a first catalyst composition
comprising a first polymerization catalyst/organic polyhydroxyl
compound mixture and a catalyst composition of a second
polymerization catalyst without a organic polyhydroxyl compound to
improve the overall process operability. In a further embodiment,
the first and second catalyst compositions described above can be
used simultaneously, for example as a mixture or injected into a
reactor separately. In any of these embodiment, the first and
second polymerization catalysts may be the same or different.
[0143] Polymerization Process
[0144] The catalysts and catalyst systems of the invention
described above are suitable for use in any polymerization process
over a wide range of temperatures and pressures. The temperatures
may be in the range of from 60.degree. C. to about 280.degree. C.,
preferably from 50.degree. C. to about 200.degree. C., and the
pressures employed may be in the range from 1 atmosphere to about
500 atmospheres or higher.
[0145] Polymerization processes include solution, gas phase, slurry
phase and a high pressure process or a combination thereof.
Particularly preferred is a gas phase or slurry phase
polymerization of one or more olefins at least one of which is
ethylene or propylene.
[0146] In one embodiment, the process of this invention is directed
toward a solution, high pressure, slurry or gas phase
polymerization process of one or more olefin monomers having from 2
to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more
preferably 2 to 8 carbon atoms. The invention is particularly well
suited to the polymerization of two or more olefin monomers of
ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1,
hexene-1, octene-1 and decene-1.
[0147] Other monomers useful in the process of the invention
include ethylenically unsaturated monomers, diolefins having 4 to
18 carbon atoms, conjugated or nonconjugated dienes, polyenes,
vinyl monomers and cyclic olefins. Non-limiting monomers useful in
the invention may include norbornene, norbornadiene, isobutylene,
isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted
styrene, ethylidene norbornene, dicyclopentadiene and
cyclopentene.
[0148] In the most preferred embodiment of the process of the
invention, a copolymer of ethylene is produced, where with
ethylene, a comonomer having at least one alpha-olefin having from
4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and
most preferably from 4 to 8 carbon atoms, is polymerized in a gas
phase process.
[0149] In another embodiment of the process of the invention,
ethylene or propylene is polymerized with at least two different
comonomers, optionally one of which may be a diene, to form a
terpolymer.
[0150] In one embodiment, the invention is directed to a
polymerization process, particularly a gas phase or slurry phase
process, for polymerizing propylene alone or with one or more other
monomers including ethylene, and/or other olefins having from 4 to
12 carbon atoms. Polypropylene polymers may be produced using the
particularly bridged bulky ligand metallocene-type catalysts as
described in U.S. Pat. Nos. 5,296,434 and 5,278,264, both of which
are herein incorporated by reference.
[0151] Typically in a gas phase polymerization process a continuous
cycle is employed where in one part of the cycle of a reactor
system, a cycling gas stream, otherwise known as a recycle stream
or fluidizing medium, is heated in the reactor by the heat of
polymerization. This heat is removed from the recycle composition
in another part of the cycle by a cooling system external to the
reactor. Generally, in a gas fluidized bed process for producing
polymers, a gaseous stream containing one or more monomers is
continuously cycled through a fluidized bed in the presence of a
catalyst under reactive conditions. The gaseous stream is withdrawn
from the fluidized bed and recycled back into the reactor.
Simultaneously, polymer product is withdrawn from the reactor and
fresh monomer is added to replace the polymerized monomer. (See for
example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036,
5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661
and 5,668,228, all of which are fully incorporated herein by
reference.)
[0152] The reactor pressure in a gas phase process may vary from
about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably
in the range of from about 200 psig (1379 kPa) to about 400 psig
(2759 kPa), more preferably in the range of from about 250 psig
(1724 kPa) to about 350 psig (2414 kPa).
[0153] The reactor temperature in a gas phase process may vary from
about 30.degree. C. to about 120.degree. C., preferably from about
60.degree. C. to about 115.degree. C., more preferably in the range
of from about 70.degree. C. to 11 0.degree. C., and most preferably
in the range of from about 70.degree. C. to about 95.degree. C.
[0154] Other gas phase processes contemplated by the process of the
invention include those described in U.S. Pat. Nos. 5,627,242,
5,665,818 and 5,677,375, and European publications EP-A-0 794 200,
EP-A-0 802 202 and EP-B-634 421 all of which are herein fully
incorporated by reference.
[0155] In a preferred embodiment, the reactor utilized in the
present invention is capable and the process of the invention is
producing greater than 500 lbs of polymer per hour (227 Kg/hr) to
about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer,
preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably
greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably
greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably
greater than 35,000 lbs/hr (15,900 Kg/hr), still even more
preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most
preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater
than 100,000 lbs/hr (45,500 Kg/hr).
[0156] A slurry polymerization process generally uses pressures in
the range of from about 1 to about 50 atmospheres and even greater
and temperatures in the range of 0.degree. C. to about 120.degree.
C. In a slurry polymerization, a suspension of solid, particulate
polymer is formed in a liquid polymerization diluent medium to
which ethylene and comonomers and often hydrogen along with
catalyst are added. The suspension including diluent is
intermittently or continuously removed from the reactor where the
volatile components are separated from the polymer and recycled,
optionally after a distillation, to the reactor. The liquid diluent
employed in the polymerization medium is typically an alkane having
from 3 to 7 carbon atoms, preferably a branched alkane. The medium
employed should be liquid under the conditions of polymerization
and relatively inert. When a propane medium is used the process
must be operated above the reaction diluent critical temperature
and pressure. Preferably, a hexane or an isobutane medium is
employed.
[0157] A preferred polymerization technique of the invention is
referred to as a particle form polymerization, or a slurry process
where the temperature is kept below the temperature at which the
polymer goes into solution. Such technique is well known in the
art, and described in for instance U.S. Pat. No. 3,248,179 which is
fully incorporated herein by reference. Other slurry processes
include those employing a loop reactor and those utilizing a
plurality of stirred reactors in series, parallel, or combinations
thereof. Non-limiting examples of slurry processes include
continuous loop or stirred tank processes. Also, other examples of
slurry processes are described in U.S. Pat. No. 4,613,484, which is
herein fully incorporated by reference.
[0158] In an embodiment the reactor used in the slurry process of
the invention is capable of and the process of the invention is
producing greater than 2000 lbs of polymer per hour (907 Kg/hr),
more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most
preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another
embodiment the slurry reactor used in the process of the invention
is producing greater than 15,000 lbs of polymer per hour (6804
Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to
about 100,000 lbs/hr (45,500 Kg/hr).
[0159] Examples of solution processes are described in U.S. Pat.
Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fully
incorporated herein by reference
[0160] A preferred process of the invention is where the process,
preferably a slurry or gas phase process is operated in the
presence of a bulky ligand metallocene-type catalyst system of the
invention and in the absence of or essentially free of any
scavengers, such as triethylaluminum, trimethylaluminum,
tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum
chloride, dibutyl zinc and the like. This preferred process is
described in PCT publication WO 96/08520 and U.S. Pat. No.
5,712,352 and 5,763,543, which are herein fully incorporated by
reference. In another preferred embodiment of the process of the
invention, the process is operated by introducing a organic
polyhydroxyl compound into the reactor and/or contacting a organic
polyhydroxyl compound with the bulky ligand metallocene-type
catalyst system of the invention prior to its introduction into the
reactor. These embodiments of this invention are described in U.S.
application Ser. No. 09/113,216 filed Jul. 10, 1998, incorporated
herein by reference.
[0161] Polymer Product of the Invention
[0162] The polymers produced by the process of the invention can be
used in a wide variety of products and end-use applications. The
polymers produced by the process of the invention include linear
low density polyethylene, elastomers, plastomers, high density
polyethylenes, low density polyethylenes, polypropylene and
polypropylene copolymers.
[0163] The polymers, typically ethylene based polymers, have a
density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in
the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the
range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the
range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in
the range from 0.910 g/cc to 0.940 g/cc, and most preferably
greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and
most preferably greater than 0.925 g/cc. Density is measured in
accordance with ASTM-D-1238.
[0164] The polymers produced by the process of the invention
typically have a molecular weight distribution, a weight average
molecular weight to number average molecular weight
(M.sub.w/M.sub.n) of greater than 1.5 to about 15, particularly
greater than 2 to about 10, more preferably greater than about 2.2
to less than about 8, and most preferably from 2.5 to 8.
[0165] Also, the polymers of the invention typically have a narrow
composition distribution as measured by Composition Distribution
Breadth Index (CDBI). Further details of determining the CDBI of a
copolymer are known to those skilled in the art. See, for example,
PCT Patent Application WO 93/03093, published Feb. 18, 1993, which
is fully incorporated herein by reference.
[0166] The bulky ligand metallocene-type catalyzed polymers of the
invention in one embodiment have CDBI's generally in the range of
greater than 50% to 100%, preferably 99%, preferably in the range
of 55% to 85%, and more preferably 60% to 80%, even more preferably
greater than 60%, still even more preferably greater than 65%.
[0167] In another embodiment, polymers produced using a bulky
ligand metallocene-type catalyst system of the invention have a
CDBI less than 50%, more preferably less than 40%, and most
preferably less than 30%.
[0168] The polymers of the present invention in one embodiment have
a melt index (MI) or (I.sub.2) as measured by ASTM-D-1238-E in the
range from 0.01 dg/min to 1000 dg/min, more preferably from about
0.01 dg/min to about 100 dg/min, even more preferably from about
0.1 dg/min to about 50 dg/min, and most preferably from about 0.1
dg/min to about 10 dg/min.
[0169] The polymers of the invention in an embodiment have a melt
index ratio (I.sub.21/I.sub.2) (I.sub.21 is measured by
ASTM-D-1238-F) of from 10 to less than 25, more preferably from
about 15 to less than 25.
[0170] The polymers of the invention in a preferred embodiment have
a melt index ratio (I.sub.21/I.sub.2) (I.sub.21 is measured by
ASTM-D-1238-F) of from preferably greater than 25, more preferably
greater than 30, even more preferably greater that 40, still even
more preferably greater than 50 and most preferably greater than
65. In an embodiment, the polymer of the invention may have a
narrow molecular weight distribution and a broad composition
distribution or vice-versa, and may be those polymers described in
U.S. Pat. No. 5,798,427 incorporated herein by reference.
[0171] In yet another embodiment, propylene based polymers are
produced in the process of the invention. These polymers include
atactic polypropylene, isotactic polypropylene, hemi-isotactic and
syndiotactic polypropylene. Other propylene polymers include
propylene block or impact copolymers. Propylene polymers of these
types are well known in the art see for example U.S. Pat. Nos.
4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117, all of
which are herein incorporated by reference.
[0172] The polymers of the invention may be blended and/or
coextruded with any other polymer. Non-limiting examples of other
polymers include linear low density polyethylenes produced via
conventional Ziegler-Natta and/or bulky ligand metallocene-type
catalysis, elastomers, plastomers, high pressure low density
polyethylene, high density polyethylenes, polypropylenes and the
like.
[0173] Polymers produced by the process of the invention and blends
thereof are useful in such forming operations as film, sheet, and
fiber extrusion and co-extrusion as well as blow molding, injection
molding and rotary molding. Films include blown or cast films
formed by coextrusion or by lamination useful as shrink film, cling
film, stretch film, sealing films, oriented films, snack packaging,
heavy duty bags, grocery sacks, baked and frozen food packaging,
medical packaging, industrial liners, membranes, etc. in
food-contact and non-food contact applications. Fibers include melt
spinning, solution spinning and melt blown fiber operations for use
in woven or non-woven form to make filters, diaper fabrics, medical
garments, geotextiles, etc. Extruded articles include medical
tubing, wire and cable coatings, geomembranes, and pond liners.
Molded articles include single and multi-layered constructions in
the form of bottles, tanks, large hollow articles, rigid food
containers and toys, etc.
EXAMPLES
[0174] In order to provide a better understanding of the present
invention including representative advantages thereof, the
following examples are offered.
[0175] The catalyst compound used in the Examples is a
dimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride
(Me.sub.2Si(H.sub.4Ind).sub.2ZrCl.sub.2) available from Albemarle
Corporation, Baton Rouge, La. A typical preparation of the
polymerization catalyst used in the Examples below is as follows:
The (Me.sub.2Si(H.sub.4Ind).sub.2ZrCl.sub.2) catalyst compound was
supported on Crosfield ES-70 grade silica dehydrated at 600.degree.
C. having approximately 1.0 weight percent water Loss on Ignition
(LOI). LOI is measured by determining the weight loss of the
support material which has been heated and held at a temperature of
about 1 000.degree. C. for about 22 hours. The Crosfield ES-70
grade silica has an average particle size of 40 microns and is
available from Crosfield Limited, Warrington, England.
[0176] The first step in the manufacture of the supported bulky
ligand metallocene-type catalyst above involves forming a precursor
solution. 460 lbs (209 kg) of sparged and dried toluene is added to
an agitated reactor after which 1060 lbs (482 kg) of a 30 weight
percent methylaluminoxane (MAO) in toluene (available from
Albemarle, Baton Rouge, La.) is added. 947 lbs (430 kg) of a 2
weight percent toluene solution of a
dimethylsilyl-bis(tetrahydroindenyl) zirconium dichloride catalyst
compound and 600 lbs (272 kg) of additional toluene are introduced
into the reactor. The precursor solution is then stirred at
80.degree. F. to 100.degree. F. (26.7.degree. C. to 37.8.degree.
C.) for one hour.
[0177] While stirring the above precursor solution, 850 lbs (386
kg) of 600.degree. C. Crosfield dehydrated silica carrier is added
slowly to the precursor solution and the mixture agitated for 30
min. at 80.degree. F. to 100.degree. F. (26.7 to 37.8.degree. C.).
At the end of the 30 min. agitation of the mixture, 240 lbs (109
kg) of a 10 weight percent toluene solution of AS-990
(N,N-bis(2-hydroxylethyl) octadecylamine
((C.sub.18H.sub.37N(CH.sub.2CH.sub.2OH).sub.2) available as
Kemamine AS-990 from Witco Corporation, Memphis, Term., is added
together with an additional 110 lbs (50 kg) of a toluene rinse and
the reactor contents then is mixed for 30 min. while heating to
175.degree. F. (79.degree. C.). After 30 min. vacuum is applied and
the polymerization catalyst mixture dried at 175.degree. F.
(79.degree. C.) for about 15 hours to a free flowing powder. The
final polymerization catalyst weight was 1200 lbs (544 kg) and had
a Zr wt % of 0.35 and an A1 wt % of 12.0.
[0178] The organic polyhydroxyl compound used where indicated in
the examples below is xylitol available from Aldrich, Milwaukee,
Wis.
Example 1
[0179] A 1-liter autoclave, equipped with a helical stirrer to
permit efficient mixing of solids, was charged under nitrogen with
100 g dry, granular high-density polyethylene and purged with
nitrogen by pressurizing and venting three times to 100 psig (689
kpag). To the reactor was then added 100 mmol triisobutyl-aluminum
by syringe. The reactor was purged with ethylene by pressurizing
and venting three times to 100 psig (689 kpag) and then heated to
80.degree. C. before bringing to a final ethylene pressure of 107
psig (738 kPag).
[0180] An injection apparatus comprising a 2" (5.1 cm) by V/4"
(0.64 cm) piece of stainless steel tubing sealed on each end with
ball valves and attached to a source of dry, pressurized nitrogen
on one end was charged with 61 mg of the supported metallocene
catalyst mixed with 6 mg dry xylitol. The apparatus was attached to
the reactor and the catalyst injected by opening both ball valves,
allowing the nitrogen to sweep the dry catalyst into the reactor.
After 30 minutes the reaction temperature was ramped to 100.degree.
C. and held for another 30 minutes. The reactor was then vented and
cooled and the resin recovered. A total of 33.2 g of new resin was
made. After sieving through a 10 mesh screen, 3.7 g of resin was
left on the screen ("rubble").
Comparative Example 2 through 8
[0181] The procedure was exactly the same as in Example 1 except
that no xylitol was mixed with the catalyst.
[0182] Table 1 below describes the "rubble" and "weight percent
rubble" produced in each of the Examples 1-6 and Comparative
Examples 7-15 above. The higher the level of rubble produced the
worse the operability of the process of the invention.
[0183] From the data provided in Table 1 below the use of the
organic polyhydroxyl compound of the invention provides for an
improved polymerization process, one that overall generates the
least amount of rubble.
1TABLE 1 Amount of Rubble Rubble Example # Compound Used Polymer
(g) (g) (weight %) 1 10%-Xylitol 33.2 3.7 11% C2 None 29.7 4.9 16%
C3 None 27.5 0.8 3% C4 None 39.7 11 28% C5 None 26.2 3.1 12% C6
None 38.2 7.6 20% C7 None 33.3 2.7 8% C8 None 38.0 12.1 32%
[0184] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to variations not necessarily illustrated herein. For
example, it is contemplated that a organic polyhydroxyl compound
can be added to reactor in addition to being contacted with the
catalyst system of the invention. It is also contemplated that the
process of the invention may be used in a series reactor
polymerization process. For example, a supported bulky ligand
metallocene-type catalyst system free of a organic polyhydroxyl
compound is used in one reactor and a supported, bridged, bulky
ligand metallocene-type catalyst system having been contacted with
a organic polyhydroxyl compound being used in another or
vice-versa. It is also contemplated that a organic polyhydroxyl
compound may be separately supported on a carrier different from
the polymerization catalyst, preferably a supported polymerization
catalyst. For this reason, then, reference should be made solely to
the appended claims for purposes of determining the true scope of
the present invention.
* * * * *